介孔ZSM-5沸石微球催化剂上萘的苄基化反应

引用本文: 苗海霞, 马丽, 马静红, 李对春, 李瑞丰. 介孔ZSM-5沸石微球催化剂上萘的苄基化反应[J]. 物理化学学报, 2014, 30(8): 1518-1526. doi: 10.3866/PKU.WHXB201405271 shu

Citation: MIAO Hai-Xia, MA Li, MA Jing-Hong, LI Dui-Chun, LI Rui-Feng. Benzylation of Naphthalene over a Mesoporous ZSM-5 Zeolite Microsphere Catalyst[J]. Acta Physico-Chimica Sinica, 2014, 30(8): 1518-1526. doi: 10.3866/PKU.WHXB201405271 shu

介孔ZSM-5沸石微球催化剂上萘的苄基化反应

基金项目:
国家自然科学基金（51272169，21246003）资助项目

摘要:

以有机硅烷化的二氧化硅为硅源，制备了由纳米粒子聚集而成的、具有晶间和晶内介孔的微球状ZSM-5（MMZ-5）沸石. 通过吡啶（Py）和2，6-二叔丁基吡啶（DTBPy）在介孔沸石表面吸附的原位红外测试，对其酸性进行了表征. 与微孔ZSM-5 沸石相比，MMZ-5 沸石上的Lewis 酸位和总酸位增加，特别是探针大分子DTBPy（动力学直径约为1.05 nm）可及的Brönsted 酸位显著提高. 萘在MMZ-5沸石上的苄基化催化结果表明，反应发生在拥有大量活性位的沸石外表面，大的沸石外表面为该催化反应提供了作用空间，从而提高了沸石活性位的有效利用率，使MMZ-5 沸石上萘的苄基化反应活性显著提高，能够生成大分子产物一苄基萘和二苄基萘；其中，一苄基萘的选择性约为79%，且随着反应时间的延长，MMZ-5 沸石大的晶内介孔（3-5 nm）为反应提供了有效反应空间，促进一苄基萘向二苄基萘转化. 异构体α-一苄基萘和β-一苄基萘的摩尔比值约为83：17，该值不随着温度和转化率的变化而改变.

关键词:

English

Benzylation of Naphthalene over a Mesoporous ZSM-5 Zeolite Microsphere Catalyst

1.
1. Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P. R. China;
2. Department of Chemistry Engineering, Jincheng Institute of Technology, Jincheng 048000, Shanxi Province, P. R. China
Received Date: 02 April 2014
Available Online: 18 July 2014
Fund Project:
国家自然科学基金（51272169，21246003）资助项目

Abstract:

A microspherical ZSM-5 zeolite aggregated from nanosized zeolite crystals with intra- and intercrystalline mesoporous structures (MMZ- 5) was prepared using presilanized silica as silica source. The acidic properties of this mesoporous zeolite were characterized via Fourier transform infrared spectroscopy (FTIR) in combination with pyridine (Py) and 2,6-di-tert-butylpyridine (DTBPy). Compared with conventional microporous ZSM- 5, the MMZ- 5 zeolite possessed more Lewis acid sites and many more accessible Brönsted acid sites for bulky DTBPy molecule (1.05 nm in diameter). This mesoporous zeolite thus afforded both effective active sites and reaction voids allowing the reaction of larger molecules, resulting in enhanced catalytic activity and stability of the MMZ-5 zeolite during the benzylation of naphthalene with benzyl chloride (BC) to form bulky monobenzylnaphthalenes and dibenzylnaphthalenes, during which the selectivity for monobenzylnaphthalenes was estimated to be about 79%. Moreover, the selectivity for dibenzylnaphthalenes was enhanced with increasing reaction time, owing to the consecutive reactions between monobenzylnaphthalenes and BC occurring at the effective reaction voids of the MMZ-5 zeolite. The distribution of the monobenzylnaphthalene isomers (α-BN and β-BN) was found to be independent of both reaction temperature and extent of BC conversion, the α-BN/β-BN molar ratio being about 83:17.

Key words:

1. [1]
  
  (1) Corma, A. Chem. Rev. 1997, 97 (6), 2373. doi: 10.1021/cr960406n
  (1) Corma, A. Chem. Rev. 1997, 97 (6), 2373. doi: 10.1021/cr960406n
2. [2]
  (2) Perez-Ramirez, J.; Christensen, C. H.; Egeblad, K.; Christensen, C. H.; Groen, J. C. Chem. Soc. Rev. 2008, 37 (11), 2530. doi: 10.1039/b809030k(2) Perez-Ramirez, J.; Christensen, C. H.; Egeblad, K.; Christensen, C. H.; Groen, J. C. Chem. Soc. Rev. 2008, 37 (11), 2530. doi: 10.1039/b809030k
3. [3]
  (3) Tao, Y.; Kanoh, H.; Abrams, L.; Kaneko, K. Chem. Rev. 2006, 106 (3), 896. doi: 10.1021/cr040204o(3) Tao, Y.; Kanoh, H.; Abrams, L.; Kaneko, K. Chem. Rev. 2006, 106 (3), 896. doi: 10.1021/cr040204o
4. [4]
  (4) Ogura, M.; Shinomiya, S. Y.; Tateno, J.; Nara, Y.; Nomura, M.; Kikuchi, E.; Matsukata, M. Appl. Catal. A 2001, 219 (1), 33.(4) Ogura, M.; Shinomiya, S. Y.; Tateno, J.; Nara, Y.; Nomura, M.; Kikuchi, E.; Matsukata, M. Appl. Catal. A 2001, 219 (1), 33.
5. [5]
  (5) Abelló, S.; Bonilla, A.; Pérez-Ramírez, J. Appl. Catal. A 2009, 364 (1), 191.(5) Abelló, S.; Bonilla, A.; Pérez-Ramírez, J. Appl. Catal. A 2009, 364 (1), 191.
6. [6]
  (6) Yu, S. X.; Yang, J. H.; Chu, N. B.; Li, G.; Lu, J. M.;Wang, J. Q. Chin. J. Catal. 2009, 30 (10), 1035. [于素霞, 杨建华, 初乃波, 李刚, 鲁金明, 王金渠. 催化学报, 2009, 30 (10), 1035. ](6) Yu, S. X.; Yang, J. H.; Chu, N. B.; Li, G.; Lu, J. M.;Wang, J. Q. Chin. J. Catal. 2009, 30 (10), 1035. [于素霞, 杨建华, 初乃波, 李刚, 鲁金明, 王金渠. 催化学报, 2009, 30 (10), 1035. ]
7. [7]
  (7) Yang, Z. X.; Xia, Y. D.; Mokaya, R. Adv. Mater. 2004, 16 (8), 727. doi: 10.1002/adma.200306295(7) Yang, Z. X.; Xia, Y. D.; Mokaya, R. Adv. Mater. 2004, 16 (8), 727. doi: 10.1002/adma.200306295
8. [8]
  (8) Shetti, V. N.; Kim, J.; Srivastava, R.; Choi, M.; Ryoo, R. J. Catal. 2008, 254 (2), 296. doi: 10.1016/j.jcat.2008.01.006(8) Shetti, V. N.; Kim, J.; Srivastava, R.; Choi, M.; Ryoo, R. J. Catal. 2008, 254 (2), 296. doi: 10.1016/j.jcat.2008.01.006
9. [9]
  (9) Choi, M.; Cho, H. S.; Srivastava, R.; Venkatesan, C.; Choi, D. H.; Ryoo, R. Nat. Mater. 2006, 5 (9), 718. doi: 10.1038/nmat1705(9) Choi, M.; Cho, H. S.; Srivastava, R.; Venkatesan, C.; Choi, D. H.; Ryoo, R. Nat. Mater. 2006, 5 (9), 718. doi: 10.1038/nmat1705
10. [10]
  (10) Park, D. H.; Kim, S. S.;Wang, H.; Pinnavaia, T. J.; Papapetrou, M. C.; Lappas, A. A.; Triantafyllidis, K .S. Angew. Chem. Int. Edit. 2009, 48 (41), 7645. doi: 10.1002/anie.200901551(10) Park, D. H.; Kim, S. S.;Wang, H.; Pinnavaia, T. J.; Papapetrou, M. C.; Lappas, A. A.; Triantafyllidis, K .S. Angew. Chem. Int. Edit. 2009, 48 (41), 7645. doi: 10.1002/anie.200901551
11. [11]
  (11) Sun, Y. Y.; Prins, R. Appl. Catal. A 2008, 336 (1-2), 11. doi: 10.1016/j.apcata.2007.08.015(11) Sun, Y. Y.; Prins, R. Appl. Catal. A 2008, 336 (1-2), 11. doi: 10.1016/j.apcata.2007.08.015
12. [12]
  (12) Xue, Z.; Ma, J.; Zheng, J.; Zhang, T.; Kang, Y.; Li, R. Acta. Mater. 2012, 60, 5712. doi: 10.1016/j.actamat.2012.06.044(12) Xue, Z.; Ma, J.; Zheng, J.; Zhang, T.; Kang, Y.; Li, R. Acta. Mater. 2012, 60, 5712. doi: 10.1016/j.actamat.2012.06.044
13. [13]
  (13) Christensen, C . H.; Johannsen, K.; Schmidt, I.; Christensen, C. H. J. Am. Chem. Soc. 2003, 125 (44), 13370. doi: 10.1021/ja037063c(13) Christensen, C . H.; Johannsen, K.; Schmidt, I.; Christensen, C. H. J. Am. Chem. Soc. 2003, 125 (44), 13370. doi: 10.1021/ja037063c
14. [14]
  (14) Mokrzycki, L.; Sulikowski, B.; Olejniczak, Z. Catal. Lett. 2009, 127 (3-4), 296. doi: 10.1007/s10562-008-9678-z(14) Mokrzycki, L.; Sulikowski, B.; Olejniczak, Z. Catal. Lett. 2009, 127 (3-4), 296. doi: 10.1007/s10562-008-9678-z
15. [15]
  (15) Bari, S. M.; Aitani, A.; Saeed, M.; Al-Khattaf, S. Top. Catal. 2010, 53, 1387. doi: 10.1007/s11244-010-9598-1(15) Bari, S. M.; Aitani, A.; Saeed, M.; Al-Khattaf, S. Top. Catal. 2010, 53, 1387. doi: 10.1007/s11244-010-9598-1
16. [16]
  (16) Batt, D. G.; Maynard, G. D.; Petraitis, J. J.; Shaw, J. E.; Galbraith,W.; Harris, R. J. Med. Chem. 1990, 33 (1), 360. doi: 10.1021/jm00163a058(16) Batt, D. G.; Maynard, G. D.; Petraitis, J. J.; Shaw, J. E.; Galbraith,W.; Harris, R. J. Med. Chem. 1990, 33 (1), 360. doi: 10.1021/jm00163a058
17. [17]
  (17) Beltrame, P.; Demartin, F.; Zuretti, G. Appl. Catal. A 2002, 232 (1), 265.(17) Beltrame, P.; Demartin, F.; Zuretti, G. Appl. Catal. A 2002, 232 (1), 265.
18. [18]
  (18) Yadav, G. D.; Purandare, S. A. J. Mol. Catal. A: Chem. 2007, 263 (1), 26.(18) Yadav, G. D.; Purandare, S. A. J. Mol. Catal. A: Chem. 2007, 263 (1), 26.
19. [19]
  (19) Bachari, K.; Cherifi, O. Appl. Catal. A 2007, 319, 259. doi: 10.1016/j.apcata.2006.12.010(19) Bachari, K.; Cherifi, O. Appl. Catal. A 2007, 319, 259. doi: 10.1016/j.apcata.2006.12.010
20. [20]
  (20) Bachari, K.; Millet, J. M. M.; Benaïchouba, B.; Cherifi, O.; Figueras, F. J. Catal. 2004, 221 (1), 55. doi: 10.1016/S0021-9517(03)00295-1(20) Bachari, K.; Millet, J. M. M.; Benaïchouba, B.; Cherifi, O.; Figueras, F. J. Catal. 2004, 221 (1), 55. doi: 10.1016/S0021-9517(03)00295-1
21. [21]
  (21) Bhattacharya, D.; Pandey, A. K.; Singh, A. P. Stud. Surf. Sci. Catal. 1998, 113, 737. doi: 10.1016/S0167-2991(98)80353-4(21) Bhattacharya, D.; Pandey, A. K.; Singh, A. P. Stud. Surf. Sci. Catal. 1998, 113, 737. doi: 10.1016/S0167-2991(98)80353-4
22. [22]
  (22) Thibault-Starzyk, F.; Stan, I.; Abelló, S.; Bonilla, A.; Thomas, K.; Fernandez, C.; Gilson, J. P.; Pérez-Ramírez, J. J. Catal. 2009, 264 (1), 11. doi: 10.1016/j.jcat.2009.03.006(22) Thibault-Starzyk, F.; Stan, I.; Abelló, S.; Bonilla, A.; Thomas, K.; Fernandez, C.; Gilson, J. P.; Pérez-Ramírez, J. J. Catal. 2009, 264 (1), 11. doi: 10.1016/j.jcat.2009.03.006
23. [23]
  (23) Zheng, S. R.; Heydenrych, H. R.; Jentys, A.; Lercher, J. A. J. Phys. Chem. B 2002, 106 (37), 9552. doi: 10.1021/jp014091d(23) Zheng, S. R.; Heydenrych, H. R.; Jentys, A.; Lercher, J. A. J. Phys. Chem. B 2002, 106 (37), 9552. doi: 10.1021/jp014091d
24. [24]
  (24) Wang,W. L.; Liu, B. J.; Zeng, X. J. Acta Phys. -Chim. Sin. 2008, 24 (11), 2102. [王文兰, 刘百军, 曾贤君. 物理化学学报, 2008, 24 (11), 2102.] doi: 10.3866/PKU.WHXB20081128(24) Wang,W. L.; Liu, B. J.; Zeng, X. J. Acta Phys. -Chim. Sin. 2008, 24 (11), 2102. [王文兰, 刘百军, 曾贤君. 物理化学学报, 2008, 24 (11), 2102.] doi: 10.3866/PKU.WHXB20081128
25. [25]
  (25) Ordomsky, V. V.; Murzin, V. Y.; Monakhova, Y. V.; Zubavichus, Y. V.; Knyazeva, E. E.; Nesterenko, N. S.; Ivanova, I. I. Microporous Mesoporous Mat. 2007, 105, 101. doi: 10.1016/j.micromeso.2007.05.056(25) Ordomsky, V. V.; Murzin, V. Y.; Monakhova, Y. V.; Zubavichus, Y. V.; Knyazeva, E. E.; Nesterenko, N. S.; Ivanova, I. I. Microporous Mesoporous Mat. 2007, 105, 101. doi: 10.1016/j.micromeso.2007.05.056
26. [26]
  (26) Xue, Z.; Zhang, T.; Ma, J.; Miao, H.; Fan,W.; Zhang, Y.; Li, R. Microporous Mesoporous Mat. 2012, 151, 271. doi: 10.1016/j.micromeso.2011.10.026(26) Xue, Z.; Zhang, T.; Ma, J.; Miao, H.; Fan,W.; Zhang, Y.; Li, R. Microporous Mesoporous Mat. 2012, 151, 271. doi: 10.1016/j.micromeso.2011.10.026
27. [27]
  (27) Serrano, D. P.; Aguado, J.; Rodriguez, J. M.; Peral, A. J. Mater. Chem. 2008, 18 (35), 4210. doi: 10.1039/b805502e(27) Serrano, D. P.; Aguado, J.; Rodriguez, J. M.; Peral, A. J. Mater. Chem. 2008, 18 (35), 4210. doi: 10.1039/b805502e
28. [28]
  (28) Serrano, D. P.; García, R. A.; Vicente, G.; Linares, M.; Procházková, D.; ejka, J. J. Catal. 2011, 279 (2), 366. doi: 10.1016/j.jcat.2011.02.007(28) Serrano, D. P.; García, R. A.; Vicente, G.; Linares, M.; Procházková, D.; ejka, J. J. Catal. 2011, 279 (2), 366. doi: 10.1016/j.jcat.2011.02.007
29. [29]
  (29) Jin, H.; Ansari, M. B.; Park, S. E. Chem. Commun. 2011, 47 (26), 7482. doi: 10.1039/c1cc12259b(29) Jin, H.; Ansari, M. B.; Park, S. E. Chem. Commun. 2011, 47 (26), 7482. doi: 10.1039/c1cc12259b
30. [30]
  (30) Gracia, M. J.; Losada, E.; Luque, R.; Campelo, J. M.; Luna, D.; Marinas, J. M.; Romero, A. A. Appl. Catal. A 2008, 349 (1), 148.(30) Gracia, M. J.; Losada, E.; Luque, R.; Campelo, J. M.; Luna, D.; Marinas, J. M.; Romero, A. A. Appl. Catal. A 2008, 349 (1), 148.
31. [31]
  (31) Chaube, V. D. Catal. Commun. 2004, 5 (6), 321. doi: 10.1016/j.catcom.2004.02.013(31) Chaube, V. D. Catal. Commun. 2004, 5 (6), 321. doi: 10.1016/j.catcom.2004.02.013
32. [32]
  (32) Coq, B.; urves, V.; Figuéras, F. Appl. Catal. A 1993, 100 (1), 69. doi: 10.1016/0926-860X(93)80116-8(32) Coq, B.; urves, V.; Figuéras, F. Appl. Catal. A 1993, 100 (1), 69. doi: 10.1016/0926-860X(93)80116-8
33. [33]
  (33) Beltrame, P.; Zuretti, G. Appl. Catal. A 2003, 248 (1), 75.(33) Beltrame, P.; Zuretti, G. Appl. Catal. A 2003, 248 (1), 75.
34. [34]
  (34) Beltrame, P.; Zuretti, G. Appl. Catal. A 2004, 268 (1), 169.
  (34) Beltrame, P.; Zuretti, G. Appl. Catal. A 2004, 268 (1), 169.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

介孔ZSM-5沸石微球催化剂上萘的苄基化反应

English

Benzylation of Naphthalene over a Mesoporous ZSM-5 Zeolite Microsphere Catalyst

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

介孔ZSM-5沸石微球催化剂上萘的苄基化反应

English

Benzylation of Naphthalene over a Mesoporous ZSM-5 Zeolite Microsphere Catalyst

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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